New azodyestuffs



Patented Mar. 7, 1933 UNITE STATES PATENT OFFICE I Lnoronn LASKA AND ARTHUR zrrsoHER, I

AssIeNoRs'ro GENERAL ANILINE woRKs, me, on Ew YORK; N.

'TIoN oE DELAWARE or OFFENBACH-ON-THE-MAIN, GERMANY,

Y., A CORPORA- NEW 'AZODYESTUFFS N0 Drawing. Application filed 0ctober 29, 1930, Serial No. 492,080, and in Germany November 5, 1929.

Our U. S. application Serial No. 472,483, filed August 1, 1930, relates to new azodyestuffs which are obtained by combining any diazotized aromatic monoamino-, diaminoor amino'azo-compound (which are thereinafter referred to for the sake of brevity as aromatic amino compound) with a 3-hydroxydiphenyl-amine-4-carboxylic acid-arylamide o; with a nuclear substitution product there- 0 Our present invention represents a special embodiment of the said invention and consists in using in the above process arylamides which contain in the aryl nucleus a hydroxy group and have, relative tothis group, at least one free ortho or para position capable of coupling with diazocompounds. ,These hydroxylated arylamides correspond to the general formula:

wherein the benzene nucleus signified by I may be substituted and Rmeans a radical of the benzene o-r naphthalene series having at least one free ortho or para position capable of coupling. 7

The combining components used in this process may be produced (in the manner described in U. S. Patent No. 1,868,612) by condensing 3 -hydroXy'- diphenylamine 4 carboXylic acid or a nuclear derivative thereof with a hydroXyla-ted arylamine of the benzene or naphthalene series of the aforesaid kind. Such hydroxylated arylamines of the benzene series are, for instance, 2- or 3- or 4-amino-l-hydroxy-benzene,

'1-hydroXy-2-amino-4-methyl-benzene,

1-hydroXy-3-amino-4-methyl-benzene,

1-hydroXy-4- amino-Q-methyl-benZene, 1-hydroXy-4-amino-3-methyl-benzene; of the naphthalene series, 3-amino-2-hydroXy-naphthalene may be mentioned.

The new dyestuffs thus obtained corre spond to the general formula I on '7 I tion Serial No. 472,483, filed August 1, 1930;

In order to further illustrate our inven t1on,'the following examples are given, the

parts being by weight and all temperatures in v centigrade degrees. We wish it, however, to be understood that we are not limited to the particular products or reaction conditions mentioned therein.

Example 20 grs of the 3-hydroxy-phenyl-amide of 4-chloro-3-hydroxy diphenyl amine-4-carboxylic acid are made to'a paste with'20cc of Turkey red oil of 50% strength and 30 cc of a caustic soda solution of 34 B. The

aste is moderately warmed and dissolved in about 300 cc of hot soft water, advantageous,- ly by boiling. By the addition of cold soft water the whole is made up to 1000 cc and then mixed with 20 grs of common salt. In this solution cotton yarn is impregnated at 30 for 30 minutes. A

The padded material is dehydrated and then developed while well handling with. a

' diazo solution prepared as follows:

1.8 grs of the hydro-chloride of 5-chloro- 2-amino-toluene are dissolved in 2 'cc of hydrochloric acid of B. and water, and diazotizedwith 0.75 grs of sodium nitrite. Then 0.9 grs of sodium bicarbonate and grs of common salt are added and the whole is made up to 1000 cc.

The developed goods are rinsed cold and hot, soaped at the boil for half an hour, rinsed hot and cold and dried.

In this manner bright yellowish brown shades are obtained.

With other diazo compounds and other hydroXy-arylamides of 3-hydroxy-phenylaryh amine-4-carboxylic acids, the process may likewise be carried out. The shades of such dyestufis are sh own in the following table:

3-hydroxy l"-methyl diphenylamine-4'- carboXy-3-aminophenol combined with the diazocompound of:

2.5- dichloraniline Yellowish brown 8-nitro-l-amino-toluene Brown 5-nitr0-2-amino-t0luene .Dark reddish brown 3'-hydroxy-4-methyl diphenylamine-4- carboxyl-aminophenol combined with the diazocompound of:

l-aminoanthraquinone Reddish brown 4 amino -3.2'-dimethyl-azobenezenei -Reddish brown i 3-hydroXy-2.-methyl diphenylamine-U- carboxy-l-aminophenol combined with the diazocmopound of: V

2.5-dichloraniline ,Yellowish' brown 4-amino -3.2'-dimethyl-azobenzene Reddish brown 3-hydroxy-4c"-meth0xy-diphenylamine-4- carboXy-3-aminophenol combined with the diazocompound of:

2.5-dichloraniline .Yellowish brown 5-chlor-2-amino-toluene .Yellowish brown Dianisidine -Blackishbrown 2.5-dichloraniline Full yellowish brown 2-nitroaniline Full brown nitro-Q-aminoanisole Full brown 3-nitro-4c-amino- 3-hydroXy-4E -chloro-diphenylamine 4L- carboxy--aminophenol combined with the diazocompound of:

2.5-dichlorztniline Yellowish brown 5-nitro-2-amino-toluene Reddish brown 4-amino-3.2-dimethylazobenzene Reddish brown Q-nitroaniline Brown 3-hydroxy-4c-chloro diphenylamine A- carboxy-G-amino-3-oXy-1-toluene combined with the diazocompound of:

2.5-dichloraniline Yellowish brown-1 3-nitro-4-a1nino-toluene Brown -nitro-Q-amino-anisolm Yellowish brown l-aminoei1thraquinone Reddish brown 8-hydroXy-4-chloro diphenylamine 4'- carboxy-2-amino-4-hydroxy-l-toluene combined with the diazocompound of:

S-chloranilihe Yellowish brown 2At.5-trichloraniline Brown t-chloro-2-amin0-toluene Yellowish brown 2.5-dichlorol-aminotoluene Brown -chloro-Q-amino-diphenyl-ether Brown 4-chloro-2-nitroaniline Reddish brown 3-hydroxy-4-chlor0 diphenylamine 4- carboXy-3-amino-4-hydroXy1-toluene combined with the diazocompound of:

2.5-dichlorani1ine Brown 4-chloro-2-amino-diphenyl-ether Brown 4-chloro-2-nitroaniline- Brown l-eminoanthraquinorR- Reddish brown 3-hydroXy 2 chloro diphenylemine -45- carboXy3-aminophenol combined with the diazocompound of 5-chloro-2-amino-toluene Yellowish brown 3-nitro-4-amino-toluene Reddish brown 4-a1nino-3.2'-dimethylazobenzene Reddish brown 3-hydroxy -2" -chloro-diphenylamine 4- carboXy-l-aminophcnol combined with the diazocompound of:

5-chloro-2-emino-toluene Yellowish brown 3-nitro-t-amino-toluene Brown 5-nitro-2-amino-anisole- Reddish brown -nitro-Q-amino-anisole Yello'wish brown 3-hydroxy -2" -chloro-diphenylamine A- carbOXy-Q-amino-3-naphthol combined with i the diazocompound of:

2.5-dicholor-aniline Yellowish brown 5-nitro-2-amino-toluene- 'Reddish brown l-emino-anthraquinonm Reddishbrown 1. As new compounds the azo-dyestuifs of the probable general formula:

wherein the benzene nucleus I may be substituted by alkyl, alkoxy or halogen, R means an aromatic radical of the benzene or naphthalene series and R means a radical of the benzene, naphthalene or anthracene series which may contain an alkyl, alkoxy, phenoxy, phenylazo or nitro-group or halogen, which compounds yield when produced on a substratum brown to black shades.

2. As new compounds the azo-dyestuffs of the probable general formula:

wherein the nucleus I may be substituted by alkyl, alkoxy, phenoxy or halogen, the nuclei IV may be substituted by alkyl, alkoxy, phe noxy, phenylazo, nitro groups or halogen and It means an aromatic radical of the benzene or naphthalene series, which compounds yield when produced on a substratum brown r shades.

3.- As new compounds the azo-dyestufls of the probable general formula:

wherein X means alkyl, alkoxy or halogen, the nuclei IV may be substituted by alkyl,

alkoxy, phenoXy, phenylazo, nitro groups or I halogen and R means an aromatic radical of the benzene or naphthalene series, which compounds yield when produced on a substratum brown shades. I

4; As new compounds the azo-dyestufi's of the probable general formula:

o o-N r -on wherein the nuclei IVv may be substituted by alkyl, alkoXy, phenoXy, phenylazo, nitro groups or halogen andR means an aromatic radical of the benzene or naphthalene series,

which compounds yield when produced on a substratum brown shades.

5. As new compounds the azo-dyestuffs of the probable general formula:

wherein the nuclei IV may be substituted by alkyl, alkoxy, phenoXy, phenylazo, nitro groups or halogen and the nucleus III may be substituted by an alkyl group, which compounds yield when produced on a substratum brown shades.

6. Asnew compounds the azo-dyestuffs of the probable general formula: I

p w OH wherein the nuclei IV may be substituted by alkyl, alkoxy, phenoXy, V phenylazo, nitro groups or halogen and the nucleus III may be substituted by an alkyl group and its azogroup occupies the para-position relative to the hydroxy-group,' which compounds yield when produced on a substratum brown shades.

7. As new compounds the azo-dyestufi's of the probable general formula:

(wherein the nuclei IV may be substituted 10, by alkyl, alkoxy, phenoxy, nitro groups or halogen, which compounds yield when produced on a substratum brown shades.

8. As a new compound the 'azo-dyestuff of the probable formula:

s OH olONn CO-NHQ 01 01 s '20 N=N N=N-Q which compound yields when produced on a substratum full yellowish brown shades.

' 9. As a new compound the azo-dyestufi of the probable formula on v p on 1 which compound yields when produced on a a O I substratum full reddish brown shades.

10. As a new compound the azodyestulf of the probable formula:

-: which compound yields when produced on a substratum dark reddish broken shades.

In testimony whereof,rwe afix our signatures.

LEOPOLD LASKA. ARTHUR ZITSCHER. 

